DE2361931A1 - LIGHT-SENSITIVE COATING DIMENSIONS AND THEIR USE - Google Patents

Description

The invention relates to photosensitive resinous compositions which are particularly suitable for many purposes, such as manufacturing lithographic plates, multicolor proofs, visuals, and printed circuit boards, and particularly concerned the invention compositions comprising a photosensitive, negative-acting or positive-acting diazonium compound and certain unsaturated monomers, which are described more specifically below, contain, these compositions as super-

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Draw on suitable base materials such as lithographic or electrically conductive metals, plastics such as Mylar09 and the like can be applied, exposed through a negative or positive transparency and with a total or im substantial total aqueous developer can be developed.

Among the numerous improvements and advantages obtained in accordance with the present invention, summarized as follows are the following to mention: the union of a light-sensitive material

th
and a long-lasting image or object-forming material which can be applied as a single coating on a suitable base, the coating (1) being more photosensitive than many other previously commercially available systems with diazo sensitization, (2) on the base material with relatively cheap, non-volatile, non-toxic, wholly or essentially wholly aqueous desensitizing or developer solutions can be developed, (3) on the base material at least the same life, shelf life, photosensitivity and durability as previously commercially available presensitized lithographic plates and in general has a significantly longer resistance to pressure,

(4) does not require hand painting after development and

(5) satisfactorily quickly and easily by relatively unskilled workers without undue care to avoid interference can be developed and thereby delivers qualitatively high-quality, sharp and fine image areas or images.

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The technique of lithographic printing, upon which the pre- ' This invention is based on the immiscibility of fat and water and makes this phenomenon take advantage of the preferential retention of a transferable, fat-like, image-forming substance on an image surface and the similar retention of an aqueous dampening liquid exploited on a corresponding non-image area. When an oleophilic image on a suitable surface and the entire surface is then moistened with an aqueous solution, the image area repels the water while the non-image area holds back the water. In the subsequent application of a grease-like printing ink on the entire On the surface, the image portion of the surface retains the printing ink, while the moistened non-image portion repels it. The ink on the image area can then be transferred to the surface of the appropriate material on which the Image is to be reproduced, such as on paper, cloth or the like. The transfer of the ink usually completes the Use of an intermediate surface, such as a so-called offset or blanket cylinder, to avoid image reversal or mirror image printing.

Lithographic plates such as those embodying the present invention is suitable to have a coating of a photosensitive Composition that adheres to a suitable base sheet material such as an aluminum sheet. if the photosensitive coating from the manufacturer on the base sheet is applied, the plate is called "presensitized

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When the photosensitive coating is applied to the base material by a lithographer or commercial plate maker, the plate is called a "wipe-on plate." Depending on the nature of the photosensitive composition used, a coated plate may be used / to directly reproduce the image with which it is exposed, in which case the plate is called positive-acting , or to reproduce an image complementary to that with which it is exposed, in which case the plate is called negative-acting In any event, the image area of the developed plate is relatively oleophilic and the non-image area is relatively hydrophilic.

A negative lithographic plate is exposed to the desired image through a negative transparency. The light causes that the exposed photosensitive material, usually a diazo compound that hardens the coating on the plate and the makes the exposed area insoluble to a desensitizing solution / which is then applied to the plate is used to remove the part of the photosensitive coating that has not been cured because the negative against the Was protected from light. The light-cured surface of a negative plate is the oleophilic surface, the one with the fatty one Ink is compatible and is referred to as "image area". The surface from which the uncured photosensitive coating is removed by the desensitizer or resulting in a hydrophilic surface with low affinity for the grease-like ink is referred to as "non-image area".

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In use, a positive plate is different such that the hydrophilic non-image area is formed in the areas of a photosensitive coating that were exposed through a positive transparency _r are either oleophilic or convertible to an oleophilic state while the unexposed areas and form the ink receptive image area.

Various attempts have been made by others to make lithographic plates using a resinous material are coated, which can be converted into a desired image so as to serve as a printing surface accepting the printing ink. Such panels, however, are either partially or totally different from those of the present invention and are commercial not satisfactory.

For example, U.S. Patent 3,136,637 describes one lithographic plate with an aluminum base sheet, a first coating of a photosensitive diazo compound the base sheet and a second different coating of resinous material thereover. The top resin layer of the Multi-coated plate is soluble in solvent and suitable as a printing surface if the non-image areas were previously removed. Such areas are removed by removing the unexposed areas of the underlying first dia'zo coating removed, literally removing the overlying layer of carcass being undermined. A problem with such panels is that they are coated due to the difference in the separate coatings can be inadvertently overdeveloped, such as removing areas of the image by undermining.

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U.S. Patent 3,211,553 describes a lithographic plate with a positive acting photosensitive coating from a positive-acting complex phosphotungstate diazonium compound and special resin materials. There are in this patent no suggestion that a corresponding negative acting plate can be obtained since this patent starts from a negative lithographic diazo compound that is chemically converted with a phosphotungstic acid must be, and there are no suggestions that monomers like those according to the present invention, are suitable. The plates are developed in such a way that the exposed areas with a substantially organic solvent medium.

Kosar suggests in his book "Light Sensitive Systems", Wiley, 1962, negative acting diazo compounds together with organic ones Colloids such as gelatin and dextrin or synthetic resins such as polyvinyl alcohol and methyl cellulose to form to incorporate lithographic coatings. However, because of their hydrophilic character, such resin materials do not form printing ink accepting, image-printing surface areas and are therefore unsuitable for making lithographic plates according to the invention.

U.S. Patent 2,826,501 describes a coating material for a lithographic plate which is a photosensitive condensation product of p-diazodiphenylamine with formaldehyde and about 9 times the amount of a water-soluble superpolyamide nylon resin contains. The condensation product and the nylon resin

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are applied as a coating from an aqueous solution, and their specific proportions are _{critical for both components (} and lie within a narrow range. In addition, an exposed plate produced according to this patent must be developed with an organic developer solution, an entirely aqueous or essentially aqueous As pointed out in US Pat. No. 3,136,637, the choice of resin materials is limited, processing difficulties arise in the preparation of the compositions, particularly in the selection and use of suitable commercial solvents which are durability during printing not much better with such plates than with other plates, and the image areas of the developed plates should be further treated or coated prior to use.

U.S. Patent 3,660,097 describes the use of compositions comprising a linear polyurethane resin and a negative or positive acting diazonium compounds contain »Some disadvantages of these masses, which go hand in hand with their advantages, are the Difficulty in dissolving the compositions in a solvent in order to apply them as a coating on a substrate. Consequently will the development of, for example, a lithographic plate to remove the non-image areas, difficult because of the lack a requirement on lithographic plates, i.e. a clear difference in solubility between the image areas and the non-image areas. Freshly coated plates that have been exposed require a fair amount of scrubbing to remove the non-image '

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to remove surfaces of the coating material. Aged panels require even longer scrubbing. Develop aqueous developers the plates, but the developer should use considerable amounts of solvents such as n-propyl alcohol, benzyl alcohol, cyclohexanone or the like, in order to successfully develop the plate so that it is pure, non-ink accepting Owns non-image areas. In many cases it has proven to be beneficial to put together a developer that uses an acid such as Phosphoric acid, to keep the background, i.e. the non-image areas on the plate, clean. Opposite lithographic Plates coated with the photosensitive compositions according to the invention are those according to the United States patent 3,660,097 "slower", i.e. they require longer exposure times.

It is an object of the present invention to provide certain photosensitive To get compositions that for the production of a picture or object surface on a suitable base material are suitable. Another object of the invention is to provide such compositions or compositions for coatings on a lithographic To get printing plate that will make better presensitized plates. It is also an object of the invention to provide lithographic To get printing plates that provide highly abrasion-resistant and wear-resistant oleophilic image surfaces and as long as printing durability. Another object of the invention is to provide presensitized negative acting or to obtain positive-acting lithographic printing plates which have light-sensitive, diazonium-sensitized coatings

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containing certain unsaturated monomers, the coatings being designed to provide an image print area accepting ink upon exposure, and the plate being stable to ordinary ambient heat and humidity during storage for prolonged periods of time. Another object of the invention is to obtain lithographic printing plates which have such coatings which can give oleophilic image areas which work long and have excellent abrasion resistance, which plates after exposure through an image transparency with solvents or with an entirely aqueous or im essentially all aqueous developer medium which removes the photosensitive coating from non-image areas and the plates do not require hand painting or other treatment of the image areas. Yet another object of the invention is to provide photosensitive, diazonium-sensitized compositions which contain certain unsaturated monomers to coat suitable base sheets with these compositions, which base sheets can then be used by exposure , development and, if necessary, further treatment to produce a variety Create useful items such as screen prints, visuals, print proofs in the course of multicolor printing, and printed circuits. These and other objects of the invention are further discussed in detail below or disclosed to those skilled in the art.

Generally speaking, the present invention relates to masses those (a) which are soluble in solvents, have a negative or positive effect, light-sensitive diazonium components that have any

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commonly used lithographic diazo compounds or reaction or condensation products of such diazo compounds with the photosensitivity of the diazo compounds not can be significantly impairing agents, and (b) certain unsaturated monomers that are the products of about two equivalents of an organic diisocyanate with about one Equivalent of an active hydrogen containing organic compound such as an alcohol or amine, preferably one Contain polyol, the latter products were then reacted with an unsaturated compound, which is an active Hydrogen atom, preferably in a hydroxyl group, such contain that this reacts with the remaining isocyanate groups. Such compositions or masses can be applied as coatings on suitable base materials, such as, for example on metals and plastics, fabrics, paper, etc., from a substantially organic solvent medium, such as storage-stable presensitization lithographic plates, printed circuit boards, presensitized Screen printing screens or presensitized paper printing mats receives. After the coated base materials have been exposed to light, the non-image areas of the coating composition can be removed from the base material removed with solvent developers or a completely or practically completely aqueous developer, the developer acting on the bonds between the lower base material and (with negative acting) the light-sensitive diazonium component in the coating or (with positive acting) the light-reacted diazonium component in the

-en
acting coating and loosening this bond and in this way

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remove the coating compound. Plates and other items according to the invention, both in the presensitized state and after exposure and development, are unusual good to excellent stability during storage and subsequent handling and use in relation to such usual deterioration factors during storage, such as moisture, heat and "dark reactions", and during use such as abrasion, decrease in oleophilicity, wear and tear Weakening of the mechanical strength, marked. Especially the excellent abrasion resistance of panels after the Invention results in unusually long press durations, such as on the order of up to about that 5 to 10 times the press life of some commercially available ones Plates. Fine, sharp, clear images and objects can be obtained on suitably coated base materials and result in high quality, accurate pressed beds. Screen printing screens, paper printing mats, color printing samples, display materials and in the case of lithographic plates, a large number of excellent reproductions.

Essentially any material currently known and commonly used as a lithographic base sheet material for printing plates is used, seems possible for use as a base material on which the photosensitive compositions according to the invention can be applied and used as a coating. Such lithographic base sheet materials are, for example those made of paper, synthetic resins and especially in the case of long-lasting, dimensionally stable plates, those made of metals.

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Of the metals commonly used, such as steel, stainless steel, zinc, aluminum, copper and chromium, sheets of aluminum are preferred for various reasons. Base, which is desirably in sheet form, the base can be treated in a manner known per se "in order to improve its property as a lithographic surface" 153 and 2,882,154 in order to achieve better bonding of the coating applied to it. An aluminum sheet can be electrolytically analyzed to produce a harder, more abrasion-resistant, and more wear-resistant surface, as described, for example, in U.S. Patent 3,440,050 and British Patent 1,235,863. It is also irtöglich to apply an intermediate coating on the base surface in order to get a stronger bond between the surface and the applied over it as a coating Diazoniumsensibilisierten composition of the invention. Intermediate bonding layers are generally formed on the plate by water-soluble silicates, or preferably salt or acid solutions of metal fluorides of the group IV B such as from Kaliumzirkonhexafluorid and the acid of that compound, applied, as in the US-Patentsehriften 2,946,683 and - 3 160 506 is described. These and other methods of treating base lithographic sheets are known in the art and can be used "in conjunction with the compositions of the invention" if desired and to advantage

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In general, the diazonium components are the photosensitive ones Coating compositions according to the invention, the negative-acting or positive-acting light-sensitive diazo compounds, the are known and commonly used in the lithographic art.

Diazo compounds with negative effects are broadly speaking diazoaromatics and more particularly diazoarylamines which may be substituted on the aromatic nucleus or on the amino nitrogen, preferably p-Diazodiphenylamine and derivatives thereof, such as, for example, condensation products of this compound with organic compounds Condensation agents that contain reactive carbonyl groups, such as aldehydes and acetals, especially condensates with compounds, such as formaldehyde and paraformaldehyde. The production such eminently suitable condensation products are in the USA patents 2 922 715 and 2 946 683.

The above diazo compounds can be prepared with suitable coupling agents are reacted in order to obtain reaction products that are at least partially soluble in organic solvents, are preferably readily soluble, and which have a not significantly lower photosensitivity than "the starting diazo compound. The reaction products are only slightly water soluble, if at all. Suitable coupling agents are generally essentially essential organic compounds that react with the water-soluble diazo compounds and thereby have an ionic character decrease the latter and make them more covalent, their photosensitivity not significantly decrease and reaction products form that are soluble in organic solvents,

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but are at most a little water-soluble. Such coupling agents, currently appear to be generally acidic aromatic compounds, such as the phosphinic acids, phosphonic acids, Sulfonic acids and carboxylic acids of benzene, toluene and naphthalene and their derivatives such as the alkali salts thereof; hydroxyl-containing aromatic compounds, such as phenols, such as diphenolic acid, Benzophenone, substituted bertzophenones, naphthols, naphthalenediols and alizarines, including sulfonic acids and sulfonic acid alkali salts thereof; and acidic aliphatic compounds such as stearic acid and ethylenediaminetetraacetic acid. Particularly suitable coupling compounds of the type described are, for example, toluenesulfonic acid, benzenephosphinic acid, 2,5-dimethylbenzenesulfonic acid, benzenesulfonic acid sodium salt, Nitrobenzene acetic acid, diphenolic acid, 2,3-naphthalenediol, naphthalene-2-sulfonic acid, l-naphthol-2- (or -4) -sulfonic acid, 2,4-dinitro-l-naphthol-7-sulfonic acid, 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, m- (p'-anilinophenylazo) -benzenesulfonic acid sodium salt, p-morpholinobenzene diazonium fluorate, Alizarin sodium monosulfonate and o-toluidine-m-sulfonic acid. Some of these coupling agents and the Preparation of coupled products thereof with photosensitive diazo compounds are disclosed in U.S. Patents 3,300,309 and 3 591 575.

The diazo components and the coupling agent are preferred reacted with one another in approximately equimolar amounts.

Positive-acting known diazo resins which can be used with advantage according to the invention include various main

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Types of photosensitive compositions a »One type are esters of a 1 ^ -diazoquinone sulfonic acid chloride or a 1,2-diazonaphthoquinone sulfonic acid chloride with a polyhydroxyphenol, the latter being a condensation product , preferably of pyrogallol and acetone *. Such esters are described in U.S. Patent 3,635,709. Another type of suitable diazo resins are esters of sulfonic acids of ortho-diazophenylenes, especially quinone (1,2) diazides. and naphthoquinone (1,2) diaicides with phenol-formaldehyde resins. Such esters are described in a number of patents, such as U.S. Patent 3,046,120 and U.S. Patent 3,188,210. Another type of suitable diazo resin are phosphotungstate diazonium salts, such as a reaction product of phosphotungstic acid with an acid salt of hexafluorophosphoric acid with condensation of para-diazodiphenylamine with formaldehyde. Such diazo resins are described in U.S. Patent 3,211,553. Other positive or negative acting diazo components known to the person skilled in the art * can also be used.

The above-mentioned unsaturated monomers used in the improved Compositions used in accordance with the invention are the subject of a US patent application filed by William Rowe. the unsaturated monomers can also contain a polymeric radical.

Generally they are the reaction products of two equivalents an organic diisocyanate with one equivalent of an active one Hydrogen-containing compound, these being intermediates then treated with an unsaturated compound

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which contains an active hydrogen atom. The mentioned active hydrogen atoms are those that have activity according to possess the Zerewitinoff test described by Kohler in J. Am. Chem. Soc, 49, p. 3181 (1927).

Examples of useful compounds with active hydrogen atoms are those in which the active hydrogen atoms are bound to oxygen, nitrogen or sulfur, i.e. the active ones Groups containing hydrogen are hydroxyl, mercapto, imino, amino, carboxyl, carbamoyl, substituted carbamoyl, Sulfo-, sulfonamido, thiocarbamoyl, substituted thiocarbamoyl and similar groups. The compound may otherwise be aliphatic, aromatic or cycloaliphatic or of a mixed type be.

Examples of the diisocyanates include the aromatic, aliphatic and cycloaliphatic diisocyanates and combinations thereof. More specific examples of the diisocyanates are 2,4-tolylene diisocyanate, m-phenylene diisocyanate, xylylene diisocyanate, A- chloro-1,3-phenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,4-tetramethylene and 1,6-hexamethylene diisocyanate, 1,4 Cyclohexylene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, methylene dicyclohexylene diisocyanate, and the like. Diisocyanates in which each of the two isocyanate groups are bonded directly to a ring are preferred because they generally react more quickly with polyols or other active hydrogen-containing compounds. Particularly preferred types are

Hu

OCN- ^ \ -CV y-NCO and OCN- / \ -C- ( Vl

( VnCO.

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Other polyisocyanates, those with more than two isocyanate groups, can also be used. You can go to different Way to be made. For example, water can be used as an active hydrogen-containing compound in the manufacture of the polyisocyanate can be used. Biuret polyisocyanates are produced in accordance with US patent specification 3 124 605, which is a compound with no more than six -NCO groups and the formula

Il

OCN-RNC-NX-R-NCO
C = O
NX
R-NCO

describes in which X is a hydrogen atom or the group -CO-NX-R-NCO and R denotes the organic radical which is obtained after the two -NCO groups have been removed from an organic diisocyanate remains, which cyclohexane diisocyanate, hexamethylene diisocyanate, Phenylene diisocyanate, lower alkyl-substituted phenylene diisocyanate, lower alkoxyphenylene diisocyanate, diphenylmethane diisocyanate, Is dicyclohexyl diisocyanate or chlorine-substituted phenylene diisocyanate, the hydrogen being the only one on the compound that reacts with an -NCO group.

The polyisocyanates may contain other substituents, although those free of reactive groups other than that Isocyanate groups are preferred. Mixtures of polyisocyanates can also be used to make the invention used to produce unsaturated monomers.

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Examples of the active hydrogen containing compounds, which are used to prepare the intermediate for the unsaturated monomers used in the invention those having aliphatic hydroxyl groups, phenolic hydroxyl groups, thiol groups, carboxyl groups, amine groups or amide groups contain. Those compounds which contain more than one active hydrogen atom per molecule are preferred.

Examples of the hydroxyl-containing compounds that are used are the alkanols with a content of about 18 carbon atoms, such as methanol, ethanol, propanol, butanol, etc., Cycloalkanols such as cyclohexanol, etc., the alkenols such as allyl alcohol, etc., and the polyols.

Examples of the polyols are the diols, triols, tetrols, etc. The monomeric diols, triols and tetrols are generally preferred.

More specific examples of the monomeric diols are ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,5-pentanediol, Hexamethylene glycol, etc. More specific examples of the monomeric triols are 2- (hydroxymethyl) -2-methyl-1,3-propanediol, trimethylolpropane, Glycerin, castor oil, etc. A more specific example of a tetraol is pentaerythritol. The polyols can also be polyesters or polyethers, the former being preferred.

Particularly preferred polyester polyols are those which result from the reaction of lactones, such as, for example, ε-caprolactones, with diols, triols and polyols of low molecular weight (up to about 2OO), such as ethylene glycol, propylene glycol, Butylene glycol and the like, diethylene glycol, dipropylene glycol and the like, glycerine, trimethylolethane, trimethylol

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propane and the like, pentaerythritol and the like.

Many of these preferred polyester polyols are commercially available, such as a diol with a molecular weight of 530, a diol with a molecular weight of 830, a diol with a molecular weight of 1250, a diol with a molecular weight of 2000, a triol with a molecular weight of 540 and a triol with a molecular weight of 800.

Other polyester polyols ■ used to form the intermediate products can be used are those classes on pages 44 to 48 in "Polyurethanes-Chemistry and Technology", Part I, Chemistry by Saunders and Frisch (Interscience, 1962) are.

Examples of the polyethers which can be used to obtain the intermediates are those set out on pages 32 to 44 of this volume. Because of their hydrophilic character are those polyethers that have a preponderance of ethyleneoxy units not preferred for use in making lithographic printing plates if that preponderance to an unacceptably low ink acceptance passes through the image areas of the coating of the plate. In a suitable recipe, however, the ethyleneoxy content cannot have an adverse effect on ink acceptance, but the hydrophilicity contributes to the ease of removal Non-image areas from an exposed lithographic plate with the aid of an aqueous developer.

The polyol can also be an epoxy resin with pendant hydroxyl groups be. . '

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Examples of the phenols that can be reacted to form the intermediate products are phenol, o-cresol, 4,4'-propylidenediphenol, 4,4'-isopropylidenediphenol etc.

Examples of the thiol compounds used to make the intermediates The monothiols, such as 1-butanethiol, 1-dodecanethiol, tert-butanethiol, etc., as well as the polythiols, can be used.

The polythlols can be simple or complex organic compounds with several pendant or terminal -SH groups per average molecule. On average, should the polythiol has 2 or more -SH groups per molecule and a viscosity range from about 100 to about 100,000 cps at 70 ° C with a Brookfield viscometer, alone or in the presence of an inert solvent, aqueous dispersant or plasticizer.

Polythiols such as aliphatic monomeric polythiols such as ethanedithiol, hexamethylene dithiol, decamethylene dithiol, tolylene-2,4-dithiol, and the like, and polymeric polythiols such as thiol-terminated ethylcyclohexyldimercaptan polymer and the like can go, but they can be adopted from a practical industrial point of view Odors are largely not accepted. Examples of the polythiol compounds which are preferred because of their relatively low odor are esters of thioglycolic acid (HS-CH ₂ COOH), o (-mercaptopropionic acid (HS-CH (CH ₃ J-COOH) and β-mercaptopropionic acid (HS-CH ₂ CH ₂ COOH) with polyhydroxy compounds such as glycols, triols, tetraols, pentaols, hexaols and the like

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Examples of the preferred polythiols are ethylene glycol bis (thioglycolate), Ethylene glycol bis (ß-mercaptopropionate), trimethylolpropane tris (thioglycolate), Trimethylolpropane-tris- (ßinercaptopropionat), Pentaerythritol tetrakis (thioglycolate) and pentaerythritol tetrakis (ß-mercaptopropionate), all of which are commercially available. A specific example of a preferred polymeric polythiol is poly (propylene ether) glycol bis (ß-mercaptopropionate), that of poly (propylene ether) glycol (such as Pluracol P-2010, Wyandotte Chemical Corp.) and ß-mercaptopropionic acid is obtained by esterification.

The preferred polythiol compounds are by a minor one mercaptan-like odor marked at the beginning.

Examples of compounds that contain carboxyl groups and can be used to prepare the intermediates, are acetic acid, cinnamic acid, ß-pheny! propionic acid, succinic acid, Adipic acid, terephthalic acid, thiodipropionic acid and the like.

Examples of the amines that reacted to form the intermediates are ammonia, ethylamine, n-propylamine, n-butylamine, n-amylamine, aniline and the like, as well as the polyamines, such as m-phenylenediamine, propylenediamine, .Ethylenediamine, 2,4-tolylenediamine and the like.

Examples of other compounds used to make the intermediates can be used are the amides, such as adipamide, etc., compounds containing mixed amino groups, such as monoethanolamine, 4-aminobenzoic acid, aminopropionic acid, etc., sulfonamide-containing compounds such as 1,4-cyclohexanedisulfonamide, 1,3-propanedisulfonamide etc.

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Examples of the olefinically unsaturated, active hydrogen-containing compounds which can be reacted with the intermediates are those which have at least one active hydrogen atom and at least one addition polymerizable olefinically unsaturated group, ie ^ .C = C ^. Those compounds containing any of these groups are preferred. Specific examples of such monomeric unsaturated compounds are those containing active hydrogen atoms in the above-mentioned groups and an unsaturated group, preferably in a terminal unsaturated group, that is, the vinyl and acrylic compounds. Examples of the active hydrogen containing groups are hydroxyl, mercapto, carboxyl and amino groups. Examples of compounds are generally those composed of carbon, hydrogen, oxygen, sulfur and / or nitrogen. Illustrative formulas of such compounds are HORCH = C ^, HSRCH = CH ₂ , HOOCRCH = CH ₀ and H ₂ NRCH = CH ₂ . It is preferred that the monomeric unsaturated compound contain from about 3 to about 12 carbon atoms. Examples of unsaturated compounds are acrylic acid, cinnamic acid, methacrylic acid, hydroxyalkyl acrylates and methacrylates such as hydroxyethyl acrylate and methacrylate, cinnamon alcohol, allyl alcohol, diacetone acrylamide, unsaturated compounds which contain secondary amino or azido groups, and the like.

Examples of the active hydrogen-containing compounds, those with the intermediate products to form diluent materials and / or plasticizers can be implemented, are those that do not have the olefinically unsaturated above

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Group contain, such as the alkanols, the phenols, the secondary amines, the carboxylic acids, etc., as well as compounds such as H ₂ NR-OH and H ₂ NR-NH-. It is preferred that the compounds

OH
contain up to about 12 carbon atoms, more preferred

up to about 18 carbon atoms.

One method that can be used to prepare the unsaturated monomers of the invention is that about two equivalents of the organic diisocyanate in a reaction vessel per equivalent of active hydrogen in the monomer, active hydrogen-containing compound there. The anhydrous diisocyanate can under an inert gas atmosphere, such as nitrogen, with the anhydrous, active hydrogen containing compound at temperatures of about room temperature to about 70 ° C are implemented. Elevated temperatures are preferred. The active hydrogen containing compound, like the polyol, must be slowly, such as partially, with stirring or. Move to the diisocyanate to be added, which on the Reaction temperature, for example to 65 + 5 ° C due to the rate of addition and / or by heating and / or by cooling, depending on the exothermic reaction. The instantaneous concentration of active hydrogen containing Compound in the reaction mixture is kept low by slowly adding it in portions, causing polymer formation is reduced or switched off. The temperature of the reaction is also kept under control and low enough so that allophonate and biuret formation and also possible vinyl polymerisation are eliminated or at a minimum

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2 3 61 ^C J 31

is held. The reaction temperature is maintained until the theoretical weight percent of free remaining isocyanate can be obtained, such as by titration of a sample from the reaction vessel is determined with dibutylamine.

When the reaction is theoretically complete, the temperature will maintained, and with stirring an equivalent of second active hydrogen containing compound which may or may not contain olefinically unsaturated groups, such as Hydroxyethyl acrylate, each equivalent of the remaining isocyanate groups on the intermediate product. When the connection contains unsaturated groups, a vinyl polymerization inhibitor such as hydroquinone is also added in an effective amount. A catalyst can preferably be added for the reaction in order to increase the rate of the reaction. Examples of the catalysts that can be used are metallic catalysts such as organometallic compounds such as Organotin compounds, for example tin (II) octoate, dibutyltin dilaurate etc., organic cobalt compounds such as cobalt naphthenate, lead compounds such as lead octoate, zinc compounds, like zinc octoate. Other known catalysts, such as mineral acids, for example hydrochloric acid, nitric acid or the like, or phosphines, can also be used. If used, an effective one should be in the response Amount to be available. The stirring or agitation is continued so long that a complete conversion is guaranteed, i.e. no free isocyanate groups remain. The reaction mixture is cooled and produces the essentially monomeric new

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en compounds according to the invention, which may or may not contain unsaturated groups, depending on the reactants.

Reverse the method of addition, i.e. adding diisocyanate to, for example Adding a polyol instead of adding the polyol to a diisocyanate results in high viscosity, high molecular weight polymers instead of the monomeric adducts according to the invention with low viscosity and low molecular weight.

The method of making those used in accordance with the invention and unsaturated monomers described above can only be used with the reactant, inhibitor and catalyst or in Presence of suitable solvents, which can then be removed, for example by vacuum stripping, or in a reaction medium of vinyl compounds, particularly unsaturated esters, preferably higher-boiling acrylates, such as Ethylhexyl acrylates, ethylene glycol diacrylate, trimethylolpropane triacrylate, Pentaerythritol tetraacrylate, etc., or a plasticizer such as those of the present invention, or dioctyl phthalate etc. as a solvent medium and plasticizer or any combination thereof.

The above description illustrates generally only one process for the preparation of the compounds according to the invention. Variations are possible and desirable in many cases. For example, only one compound containing monoactive hydrogen can be used and react them in one stage with the diisocyanate. The intermediate product with isocyanate end groups is thereby formed not in a separate stage, but temporarily in a reaction leading to the end product.

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The unsaturated monomers with which the solvent-soluble, photosensitive diazonium compounds described above to form the coating wet for the production of Plates and objects according to the invention can be incorporated, perfectly meet the special requirements of Technique of making lithographic plates as they are compounds or resins or crosslink to those which are oleophilic Have character and therefore adequately accept printing inks and good differentiation from hydrophilic non-image areas result, are film formers or are compatible with film formers that are in common organic solvents soluble, but essentially or completely insoluble in water, and physically and chemically with the photosensitive Diazonium components are compatible. In addition, the unsaturated monomers can be incorporated in masses that form good continuous films, have excellent abrasion resistance, sufficiently hard for long periods of wear and tear Pressure and a sufficient degree of elasticity and flexibility without brittleness, in turn, have long durability in printing. Chemical and physical stability, as compared to the conditions of printing in offset presses and to the chemicals and inks that are used in conjunction therewith are also important properties that are possess the unsaturated monomers and their crosslinked reaction products.

The inclusion of fatty acid residues, such as those containing about 6 to about 18 carbon atoms, in the photopolymer

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236-931

sizable masses improve the oleophilic properties of those Masses for special purposes, such as for printing inks and lithographic plates.

It is possible to harden coatings of the present compositions. For example, with appropriate means in, masses that are unsaturated Containing monomers, the monomers can be crosslinked or cured and / or during exposure to actinic light cured by heat instead of actinic light or before or after exposure to actinic light. Hardening improved in general the properties such as abrasion resistance, the binding to the substrate and the cohesive character of the coating. Hardening agents for this purpose are used in small amounts, i.e. in amounts less than about 5% by weight. of the unsaturated monomer and generally less than about 1% and are, for example, peroxides such as dicumyl peroxide and the same. The more stable peroxides are preferred.

A solvent can be used to blend the unsaturated monomer and the photosensitive diazonium components and around them as an integral composition on a suitable base sheet to form an article according to the invention, such as a presensitized lithographic plate. A suitable solvent should desirably dissolve both the unsaturated compound and the diazo compound at least to the extent that that a commercially useful coating solution is formed, a solution in which the resin and the diazo compound are compatible kept in the proportions desired for the coating

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- 23 -

when the coating is subsequently made on a base sheet the solution is formed. As indicated above, the photosensitive diazonium compound is also in organic solvent soluble, the degree of solubility often depending on the particular solvent. Lots of usual organic ones Solvents dissolve both the monomer and the diazo compound sufficient on. Certain solvents are particularly beneficial for making coating solutions more specifically Combinations of the monomer and a diazonium component.

Practical organic solvents, alone or in combination are used with others and are thus currently preferred for the invention are, for example. Dimethylformamide, dimethyl sulfoxide, butyl carbitol, methyl cellosolve, Methyl cellosolve acetate, ketones such as acetone, methyl ethyl ketone and cyclohexanone, ethers such as trioxane and dioxane, and heterocycles such as tetrahydrofuran, pyridine and isophorone. Methylcellosolve and methyl ethyl ketone are particularly suitable solvents for this use.

Different relative amounts of unsaturated monomer diazonium compounds can be incorporated into the coating mass. Even if the monomer content of the coated image area increases is small, you can generally make a satisfactory printing plate, but you can take full advantage of the present invention not obtained. The desired abrasion resistance and wear resistance, which is provided by the unsaturated monomer component in the coating for an excellent long printing durability is obtained with a ■

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BATH ORIGINAL

Plate will not be sufficient on which the image areas are not that component included. On the other hand, if the salary of the Component is too large, the photosensitivity of the coating composition be insufficient for an effective and practically usable plate. Because the developer in the coating is unsaturated Monomer and diazonium compound must penetrate in order to break the bond between the coating and the base and so the To remove non-image area, a high level of monomer also reduces development ease and development time. Another factor that makes too much resin unfavorable, which on the surface might seem desirable, is that there would not be enough diazonium compound to remove from the developer for easy removal of the no-image areas to be attacked.

Based on the above considerations, it currently appears possible to provide useful articles with compositions of unsaturated Produce monomer and diazonium compound according to the invention, the about IO to 95% by weight of the 'in saturated Monomer component included. A more practical and desirable range is between about 20 and about 60% of this component, preferably at about 20 to 50% for a negative acting diazonium compound and at about 33 to about 60% for a positive acting diazonium compound.

In many cases it is preferred to use the present masses Resins and adhesives or adhesives blend to make the bond the mass applied as a coating on the substrate to enhance. Suitable materials for this purpose are for example

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wise polyethylene oxides, such as Polyox ^ resins from Union Carbide Corp., aromatic oxide resins such as phenoxy resin from Union Carbide Corp., polyamides, such as Zytel ^ ⁷ resins from EI duPont, phenol

(R)

Formaldehyde resin such as Bakelite ^ phenolic resins from Union Carbide Corp., acrylic resins such as Acryloid ^ resins from DI duPont, Harn j , _w resins from Rohm and Haas

Co., as well as hydroxyethyl cellulose, such as Cellosize ^ resins of the Union Carbide Corp. The amounts of those resins can be from about 10% to about 100% by weight based on the weight of the unsaturated monomer, while the addition of resins to the coating composition tends to reduce the durability of a board to improve while pressing, the plating can also by adding reinforcing fillers, such as synthetic silicas such as Syloid ^ from W.R. Grace Co., reinforced and improved in terms of the appearance and character of the surface. To achieve a more uniform surface coverage, to obtain, the addition of anionic surface-active agents to the masses can be beneficial, such as

IR)

se from Alcolec ^ of the American Lecithin Co. The coatings can appropriately colored by incorporating a dye and / or a pigment dispersion.

There can be different amounts of bulk with unsaturated

on

Monomer and diazonium compound / the unit area of the substrate are applied as a coating. The thickness of the finished Image or object area on the object or the plate vary with the coating weight. Too small an amount results too little material in the image area. That way becomes a

A09825 / 1060

shorter durability and resistance during pressing reached than it is otherwise available. Exits too much of the crowd however, thick coatings that are more difficult to develop and into which light can penetrate during exposure is either insufficient or takes an unnecessarily long time, especially from an economic point of view. Coverings in "one

Amounts of from about 25 mg to about 500 mg per 929 cm (per foot) of the easi bow surface give a satisfactory balance between those parameters. A preferred range is

at about 100 to 250 mg of the mass per 929 cm.

The coating thickness depends mainly on the concentration the coating solution and the mechanical means by which the coating is applied to the base sheets. For example, in a continuous process in which a roll of aluminum sheet is fed through a coating container, must for each special system the speed of the sheet, the container length, the subsequent drying time and drying temperature and solvent volatility will be billed. The concentration of the coating solution can vary. Currently about 1 to 20 parts of unsaturated monomer becomes and diazonium compound used per 100 parts of solvent, good results have been obtained at concentrations of from about 3 to about 10 parts thereof.

A presensitized lithographic plate or other item, which were produced in accordance with the above specifications can be exposed through an image transparency, and the non-image areas can be removed by developing the plate.

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The methods and facilities for exposure and development of the exposed plate are those which are known per se and in are common in the lithographic technique.

Although the mechanism of the required reactions in the diazonium coitiponents is not clearly understandable? does it seem so? dai3 the reaction or the reactions, a sufficient difference between the belichtsten and unexposed areas on the Platts cause "Thus, the DI® developers = solution a distance of l-Tichtbildbereiciie effected * without the Bildbersichs 3n2ugrei £ © n ₃ In the case of a negative-acting Diazcniumverbindung can one or more different reactions in the exposed "image area occur" at this zn harden and make it more resistant to the developer = for example, the Diasonlumverbindung with the unsaturated monomer by a free radical mechanism or some other mechanism react * perhaps to form crosslinks, or it can react with itself. Although similar reactions can also occur in positive-acting diazonium components , it seems more likely that the light-stimulated reaction makes these compounds more receptive to the developer solution.

However, an important advantage of some of the panels of the invention is that they are completely or substantially completely Aqueous developer media can be used, to the fibersug from unsaturated monomer and diazonium compound in to remove the non-image areas "To facilitate development, it is possible and usually preferred * in that

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Water to include a developing agent, such as a wetting agent, which enables the water to more easily penetrate the coating composed of the mass of unsaturated monomer and dlazonum compound, loosening the coating from the base and thus removing the coating in the non-image areas. Such means are advantageously used in order to shorten the time required for developing the plate and in this way reduce laboratory costs WAQ, which are aqueous solutions of lauryl sodium sulfate from duPont, tergitol, nonionic and anionic polyglycol ethers, and sulfated linear alcohols from Union Carbide Corp. soitfie Tween, fatty acid ester of anhydrous sorbitol from Atlas Powder Coο Good results can be achieved when using a cement in an amount of the order of up to about 15 weight = ^ water, such as up to about 5% (30 weight ~ S ~ Ige Lö · = resolution) of a commercial wetting agent such as Dupanol WAQ or up to about 10% trisodium phosphate, achieve "also useful are the developers masses in the US Patent Application Serial No. 302 994, 303 072 and 3O3 071 =

It is also possible to use a small amount of an organic solvent to be used in the aqueous developer, especially for developing plates coated with compositions which contain a relatively large proportion of unsaturated monomer compared to the diazonium component. Such solvents assist the removal of the coating by softening the resin contained therein. In general, the development time is short enough

4.0982 5/1060

and the concentration of organic solvent is ir- derr. Developer low enough so that nothing happens to the image area, until sä about. 5% by weight organic solvent. And in some cases up to about. OK I konnsK. with, advantage used "^ ezasna un? to obtain an improved developer effectiveness" typical organic solvents are, for example, low-molecular® Al = alcohols - such as isopropanol v, nah Cjcloheii & nol ,, esters _f like B'c-ijrlaoe-cst-r Kthar, like Methylcellosolve;. Ketonsp wi © Cyslohesianoii and Äs-stoa ^ and Dowanol, P-Mxj: ^ a PolypropyleiiglycoiÄt-hssr ά-if r3c Chsmical.Cyclohexanone is be ^ orziagtss solvent =

In the following examples,? J..sn are all parts and percentages Parts by weight and Ge-v

Example 1

One surface of an aluminum slat was brushed scarred, anodized and chemically underneath with sodium silicate solution Formation of a coating treated as an intermediate layer in the finished plate serves «, the treated plate surface was then with the help of a vortex with a light-sensitive Coated coating, which consisted of the following ingredients: 1 part of sensitizer (addition product of 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and para-diazodiphenylamine-formaldehyde condensate), 2 parts of a compound which is the essentially monomeric reaction product of one mole of castor oil and 3 moles of tolylene diisocyanate with the formation of an intermediate product with isocyanate end groups, which is then mixed with 3 moles of 2-hydroxyethyl acrylate has been implemented is ;, 5 parts of a compound, which is the essentially monomeric reaction product of 1 mole of tri-

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_ 35 -

methylolpropane and 3 moles of tolylene diisocyanate to form one

see
Intermediate product with isocyanate end groups, which was then reacted with 3 mol of 2-hydroxyethyl acrylate, and 0.1 part of Basic Blue Dyue 5G (available from General Dyestaffs, Color Index No. 1) »The coating was made from a 5% - igen solution in a solvent mixture of 60% methyl cellosolve, 30% ethylene dichloride and 10% dimethylformamide applied. When dry, the coating on the plate weighed about 100 mg

2 7
929 cm each (each foot). After exposing the plate in an instant frame to ultraviolet light for 1 minute through a negative transparency, the unexposed areas of the plate could easily be removed with the aqueous developer No. 922 from the Polychrome Corporation, giving commercially useful lithographic plates.

The development method consisted of hand application by the developer with an application pad. The gray scale was contiguous 6 and stretched 10o The gray scale used is a continuous -21-step gray tone sequence “the Stouffer Graphic Arts Equipment Company (South Bend, Indiana) is available.

A printing test was carried out in such a way that the plate on a Chief 22 lithographic press that was 0.15mm "Overpacked" was, by which it is meant that the plate was underlayed 0.15 mm higher than normal, was attached, whereby effected became that the plate came into contact with a greater pressure, than normally applied, overpack causes excessive wear on the plate compared to one

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normally set printing press. The rinse solution contained 35% isopropanol. usually no more flushing solutions contain than 25% alcohol. The more alcohol there is in the rinsing solution, the greater the adverse effect on the image surface of the plate. which can be expected. The ink used was Chromatone No. 4559 (a product of Chromatone Printing Ink Company, a subsidiary of the Polychrome Corporation). The paper used was 70 pound white offset paper, three times a maximum has been reused. 20,000 good copies were printed.

Example 2

Example 1 was repeated, but the aluminum was coated with potassium zirconium fluoride rather than treated with sodium silicate. The results were similar.

Example 3

Example 1 was repeated, but the aluminum was chemically etched, anodized and treated with sodium silicate. The results were similar.

Example 4

Example 1 was repeated except that 3 parts of the sensitizer, 2 parts of the second component, 7 parts of the third component and 0.1 part Calco Spirit Blue Base N dye (American Cyanamid, Color Index 42775) is used. The results were similar.

Example 5

Example 1 was repeated, but the coating also contained 2 parts Formvar 12/85 resin. The results were similar.

409825 / 10.6 0

Example 6

Example 1 was repeated, but the composition of the coating was as follows:

2 parts sensitizer

1 part glycidyl ether polyepoxide

1/2 part Formvar 12/85

1 part of the third component of the recipe in example 1

0.1 part Basic Blue dye

The exposure took place for 1 minute in a Nu Are mercury lamp housing, and it was developed as in Example 1. The gray scale was contiguous 6 and stretched 11. Overall 45,000 impressions were obtained on the overpacked printing press. When checking the plate and the printed copies there was no wear and tear on the image, and the gray scale was only half a step down from the original.

Example 7

Example 1 was repeated, but with the following recipe:

1 part sensitizer

5 parts of Reakt.ionsproduktes (A) from one mole of castor oil and 3 moles of tolylene diisocyanate with isocyanate end groups and (B) 3 moles of 2-hydroxyethyl methacrylate

4 parts of the reaction product (A) of the intermediate product with an isocyanate end group formed from one mole of caprolactone diol (Niax 510, molecular weight 530, Union Carbide) and 2 moles of 4.4 ^l -methylene bis (cyclohexyl isocyanate) and (B) 2 moles of allylamine

0.2 parts of Calco Spirit Blue Base N-paring agent

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After the coating has dried for 5 minutes with infrared lamps at 150 ° C., the plate was exposed to a xenon lamp through a negative transparency for 30 seconds. The development took place with Polychrome Corporation Aqueous Developer No. 923. The plate was gummed in the usual manner and there were 5000 good copies printed on the overpacked printing press.

Example 8

Example 1 was repeated, but the second component was replaced by the reaction product (A) of the 1 mol castor oil and 3 mol Tolylene diisocyanate formed intermediate with isocyanate end groups and (B) replaces 3 moles of methyl cellosolve. A good printing plate was obtained.

Example 9

Example 1 was repeated, but the negative acting sensitizer was replaced by 3 parts of a positive acting sensitizer that is described in US Pat. No. 3,635,709.

2 and a coating weight of 200 mg per 929 cm

(per foot) used. After drying, exposure was carried out through a positive transparency for 2 1/2 minutes in a Nu Arc lamp housing and developed with Developer No. 985 from Polychrome Corporation using a lithographic printing well suited for printing Plate received.

409825/1 060

Claims (1)

Claims 1. More photosensitive, essentially solvent-soluble, film- ^: forming coating compound, characterized in that it. . _: a) a reaction product. (A) a reaction product of about 1 equivalent of an organic monomeric hydrogen-containing Compound with 2 equivalents of an organic polyisocyanate obtained isocyanate-containing intermediate and (B) a saturated or olefinically unsaturated monomeric, active hydrogen-containing compound, where at least one of the active hydrogen-containing compounds contains only one active hydrogen atom, b) a light-sensitive, essentially solvent-soluble Component that is a negative-acting or positive-acting diazonium compound, and c) optionally a compound which is at least one polymer Contains risbaren ethylenically unsaturated group, wherein of the components a) and c) contain at least one is the at least one polymerizable unsaturated group contains. 2. coating composition according to 'claim 1, characterized in that the organic polyisocyanate tolylene diisocyanate, hexamethylene diisocyanate H II -v \> - C ~ V V-NCO or OC> J- () -C- </ -NCO is.. 409825/1060 3. coating composition according to claim 1 and 2, characterized in that at least the organic monomeric / active hydrogen-containing compound used to form the intermediate product contains two active hydrogen atoms and the compound containing active hydrogen reacted with the intermediate product contains an active hydrogen atom. 4. coating composition according to claim 1 to 3, characterized in that the compound used to form the intermediate is a polyol, a polycarboxylic acid or a hydroxy carboxy compound is. 5. Coating composition according to claim 4, characterized in that the polyol is trimethylolethane, trimethylolpropane or castor oil. 6. coating composition according to claim 3, characterized in that the an active hydrogen-containing compound oils f inically unsaturated , has a hydroxyl, carboxyl, or amino group and contains about 2 to 20 carbon atoms. 7. A coating composition according to claim 6, characterized in that the compound containing an active hydrogen is hydroxyethyl acrylate or hydroxyethyl methacrylate. 8. coating composition according to claim 1 to 7, characterized in that the compound a) contains at least one olefinically unsaturated compound. 9. coating composition according to claim 1 to 8, characterized in that it contains a polymerizable mono-ethylenically unsaturated monomer as compound c). A09825 / 1060 10. coating composition according to claim 1 to 9, characterized in that they as compound c) a crosslinker with at least two ethylenic Contains unsaturated groups. 11. Coating composition according to claim 10, characterized in that it contains the crosslinker in an amount of up to about 90, preferably up to about 50% by weight of the mass. 12. Coating composition according to claim! to 11, characterized in that it contains a vinyl polymerization inhibitor in an amount of 50 to 1,000 ppm. 13. coating composition according to claim 1 to 12, characterized in that they are a preformed compatible condensation or addition polymer in an amount up to about 20% by weight by weight contains. 14. Coating composition according to claim 1 to 13, characterized in that it contains an inorganic filler in an amount up to about 40% by weight of the mass. 15. Coating composition according to claim 1 to 14, characterized in that they a liquid or semi-liquid plasticizer in a plasticizing Amount contains. 16. Coating composition according to claim 15, characterized in that it as plasticizer a saturated or monoolefinically unsaturated, Compound of those named as compound a) contains. 17. Coating composition according to claim 1 to 16, characterized in that it contains a pigment or a dye. 409825/1060 18 ". Coating compound according to Claims 1 to 17, characterized in that it contains, as a hardening agent, a peroxide in an amount up to about 5% by weight of the unsaturated compounds in the mass. 19. Coating composition according to claim 1 to 18, characterized in that they the unsaturated components in an amount of about IO to 95, preferably in an amount of about 20 to 60% by weight of the Contains mass. 20. Coating composition according to claim 1 to 19, characterized in that the photosensitive component is a negative-acting diazonium compound is and the mass on a substrate sheet from a. Solution in an organic solvent or an essentially organic solvent medium can be applied. 21. Coating composition according to claim 20, characterized in that the Diazonium compound a light-curable, substantially water-insoluble reaction product (A) of a water-soluble, light-sensitive condensation product of a diazonium compound and an organic condensation agent therefor and (B) a water-insolubilizing organic coupling agent for this condensation product. 22. Coating composition according to claim 20, characterized in that the Diazonium compound a diazoaromatic compound, preferably a diazoarylamine compound, particularly p-diazodiphenylamine is. 23. Coating composition according to claim 21, characterized in that the organic condensation agent for the diazonium compound contains a reactive carbonyl group and preferably an aldehyde or Acetal, especially formaldehyde or paraformaldehyde, is. 409825/1060 24. Coating composition according to claim 21, characterized in that the organic coupling agent for the condensation product an acidic aromatic compound, a hydroxyl-containing aromatic compound or an acidic aliphatic compound. 25. Coating composition according to claim 21, characterized in that the organic coupling agents for the condensation product Phosphinic acid, phosphonic acid, sulfonic acid or carboxylic acid of Benzene, toluene or naphthalene, an alkali salt thereof, a hydroxyl-substituted benzene, naphthalene or anthraquinone, a Sulphonic acid or an alkali sulphonate thereof, an aliphatic one Fatty acid or a polycarboxylaminoalkane. 26. Coating composition according to claim 21, characterized in that the organic coupling agents for the condensation product toluenesulfonic acid, Benzenephosphinic acid, 2,5-dimethylbenzenesulfonic acid, Benzenesulfonic acid sodium salt, nitrobenzene acetic acid, diphenolic acid, 2,3-naphthalenediol, naphthalene-2-sulfonic acid, 1-naphthol-2-sulfonic acid, l-naphthol-4-sulfonic acid, 2,4-dinitro-l-naphthol-7-sulfonic acid, 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-Tetrahydroxybenzophenone, 2-Hydroxy-4-Kiethoxybenzophenone-5-sulfonic acid, m- (p -anilinophenylazo) benzenesulfonic acid sodium salt, p-morpholinobenzene diazonium fluorate, alizarin sodium monosulfonate, o-toluidine-m-sulfonic acid, stearic acid or ethylenediaminetetraacetic acid. 27. Coating composition according to claim 1 to 26, characterized in that the light-sensitive component is a positive-acting diazonium compound and the composition is a solution in an organic one Solvents or essentially organic solvents telmedium can be applied as a coating. ■ 409825/1060 23. Coating composition according to claim 27, characterized in that the Diazonium compound, an ester of 1,2-diazoquinone or one 1 ^ -Diazo-naphthoquinone sulfonic acid chloride with a polyhydroxyphenyl, is preferably with a condensation product of pyrogallol and acetone. 29. Coating composition according to claim 27, characterized in that the Diazonium compound is an ester of an ortho-diazophenyl sulfonic acid with a phenol formaldehyde resin. 30. wet coating according to claim 29, characterized in that the ortho-diazophenyl a quinone-1,2-diazide or a naphthoquinone-1,2-diazide is. 31. Coating composition according to claim 27, characterized in that the Diazonium compound a phosphotungstate diazonium salt, preferably is a reaction product of phosphotungstic acid with an acid salt of eexafluorophosphoric acid or with a condensation product of para-diazodiphenylamine with formaldehyde *. 32. coating composition according to claim 1 to 31, characterized in that it contains a curing agent for the unsaturated compound. 33. coating composition according to claim 1 to 32, characterized in that it contains a resin binder for the mass. 34. Coating composition according to claim 33, characterized in that it as a resin binder a polyethylene oxide , an aromatic oxide, -resin
a polyamide, a phenol formaldehyde, an acrylic resin, a urea formaldehyde resin or a hydroxyethyl cellulose, preferably in an amount of about 10 to 100% by weight, based on the weight of the polyurethane resin component. 409825/1060 35. Use of a coating composition according to claims 1 to 34 for lithographic Printing plates, illustrative materials, color proofs, or printed circuits. 4098 2 5/1060